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DC Field | Value | Language |
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dc.citation.endPage | 2885 | - |
dc.citation.number | 7 | - |
dc.citation.startPage | 2873 | - |
dc.citation.title | INORGANIC CHEMISTRY | - |
dc.citation.volume | 45 | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.contributor.author | Furutachi, Hideki | - |
dc.contributor.author | Fujinami, Shuhei | - |
dc.contributor.author | Tosha, Takehiko | - |
dc.contributor.author | Ohtsu, Hideki | - |
dc.contributor.author | Ikeda, Osamu | - |
dc.contributor.author | Suzuki, Akane | - |
dc.contributor.author | Nomura, Masaharu | - |
dc.contributor.author | Uruga, Tomoya | - |
dc.contributor.author | Tanida, Hajime | - |
dc.contributor.author | Kawai, Toshihide | - |
dc.contributor.author | Tanaka, Koji | - |
dc.contributor.author | Kitagawa, Teizo | - |
dc.contributor.author | Suzuki, Masatatsu | - |
dc.date.accessioned | 2023-12-22T10:06:54Z | - |
dc.date.available | 2023-12-22T10:06:54Z | - |
dc.date.created | 2020-09-01 | - |
dc.date.issued | 2006-04 | - |
dc.description.abstract | The reaction of [Ni-2(OH)(2)(Me-2-tpa)(2)](2+) (1) (Me-2-tpa = bis(6-methyl-2-pyridylmethyl) (2-pyridyl methyl)amine) with H2O2 causes oxidation of a methylene group on the Me-2-tpa ligand to give an N-dealkylated ligand and oxidation of a methyl group to afford a ligand-based carboxylate and an alkoxide as the final oxidation products. A series of sequential reaction intermediates produced in the oxidation pathways, a bis(mu-oxo)dinickel(Ill) ([Ni-2(O)(2)(Me-2-tpa)(2)](2+) (2)), a bis(mu-superoxo)dinickel(II) ([Ni-2(O-2)(2)(Me-2-tpa)(2)](2+) (3)), a (mu-hydroxo)(mu-alkylperoxo)dinickel(II) ([Ni-2(OH)(Me-2-tpa)(Me-tpa-CH2OO)](2+) (4)), and a bis(mu-alkylperoxo)dinickel(II) ([Ni-2(Me-tpa-CH2OO)(2)](2+) (5)), was isolated and characterized by various physicochemical measurements including X-ray crystallography, and their oxidation pathways were investigated. Reaction of 1 with H2O2 in methanol at -40 degrees C generates 2, which is extremely reactive with H2O2, producing 3. Complex 2 was isolated only from disproportionation of the superoxo ligands in 3 in the absence of H2O2 at -40 degrees C. Thermal decomposition of 2 under N-2 generated an N-dealkylated ligand Me-dpa ((6-methyl-2-pyridyl methyl) (2-pyridyl m ethyl) a mine) and a ligand-coupling dimer (Me-tpa-CH2)(2). The formation of (Me-tpa-CH2)(2) suggests that a ligand-based radical Me-tpa-CH2. is generated as a reaction intermediate, probably produced by H-atom abstraction by the oxo group. An isotope-labeling experiment revealed that intramolecular coupling occurs for the formation of the coupling dimer. The results indicate that the rebound of oxygen to Me-tpa-CH2. is slower than that observed for various high-valence bis(mu-oxo)dimetal complexes. In contrast, the decomposition of 2 and 3 in the presence Of 02 gave carboxylate and alkoxide ligands, respectively (Me-tpa-COO- and Me-tpa-CH2O-), instead of (Me-tpa-CH2)(2), indicating that the reaction of Me-tpa-CH2. with O-2 is faster than the coupling of Me-tpa-CH2. to generate ligand-based peroxyl radical Me-tpa-CH2OO... Although there is a possibility that the Me-tpa-CH2OO. species could undergo various reactions, one of the possible reactive intermediates, 4, was isolated from the decomposition of 3 under O-2 at -20 degrees C. The alkylperoxo ligands in 4 and 5 can be converted to a ligand-based aldehyde by either homolysis or heterolysis of the O-O bond, and disproportionation of the alclehyde gives a carboxylate and an alkoxide via the Cannizzaro reaction. | - |
dc.identifier.bibliographicCitation | INORGANIC CHEMISTRY, v.45, no.7, pp.2873 - 2885 | - |
dc.identifier.doi | 10.1021/ic0514243 | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.scopusid | 2-s2.0-33645911190 | - |
dc.identifier.uri | https://scholarworks.unist.ac.kr/handle/201301/48160 | - |
dc.identifier.url | https://pubs.acs.org/doi/10.1021/ic0514243 | - |
dc.identifier.wosid | 000236476700014 | - |
dc.language | 영어 | - |
dc.publisher | American Chemical Society (ACS) | - |
dc.title | Sequential Reaction Intermediates in Aliphatic C−H Bond Functionalization Initiated by a Bis(μ-oxo)dinickel(III) Complex | - |
dc.type | Article | - |
dc.description.isOpenAccess | FALSE | - |
dc.type.docType | Article | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.subject.keywordPlus | FE-2(MU-O)(2) DIAMOND CORE | - |
dc.subject.keywordPlus | NONHEME DIIRON ENZYMES | - |
dc.subject.keywordPlus | SIDE-ON PEROXO | - |
dc.subject.keywordPlus | DIOXYGEN ACTIVATION | - |
dc.subject.keywordPlus | STRUCTURAL-CHARACTERIZATION | - |
dc.subject.keywordPlus | METHANE MONOOXYGENASE | - |
dc.subject.keywordPlus | BIS(MU-OXO)DICOPPER(III) COMPLEX | - |
dc.subject.keywordPlus | ALKYLPEROXO COMPLEX | - |
dc.subject.keywordPlus | RESONANCE RAMAN | - |
dc.subject.keywordPlus | 1ST SYNTHESIS | - |
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